Preparation of graft, block and crosslinked unsaturated polymers and copolymers by olefin metathesis

ABSTRACT

The method is disclosed for preparing graft and block copolymers and interpolymers comprising subjecting two dissimilar polymeric substances to catalysts capable of inducing the olefin metathesis reaction.

United States Patent Scott et al. June 24, 1975 I PREPARATION OF GRAFI",BLOCK AND {56] References Cited CROSSLINKED UNSATURATED UNITED STATESPATENTS POLYMERS AND COPOLYMERS BY 2,933,480 4/1960 Gresham et al H260/805 OLEFIN META'IHESIS 3,331,793 7/1967 Souf'fie 260/4 [75]Inventors: Kenneih w. Scott, cuyahoga Fans; 3.439.057 4/[969 Calderon260/93.l

Nissim Calderon, Akron, both of FOREIGN PATENTS OR APPLICATIONS Ohio1,035,282 6/[966 United Kingdom 260/93.]

[73] Assignee: The Goodyear Tire & Rubber Company, Akron, Ohio PrimaryExaminer-Murray Tlllman Assistant Examiner-J. Ziegler [22] F'led: June1972 Attorney, Agent, or FirmF. W. Brunner; J. Y. 21 Appl. No.: 259,881Clowney Related U-S. Application Data [62] 5 23 5 2? The method isdisclosed for preparing graft and block copolymers and interpolymerscomprising subjecting I two dissimilar polymeric substances to catalystscapable of inducing the olefin metathesis reaction.

260/880 R; 260/880 B; 260/887 [5i] Int. Cl C08d 9/10 [58] Field ofSearch 260/889, 878 R, 878 B, 9 Claims, No Drawings PREPARATION OFCRAFT, BLOCK AND CROSSLINKED UNSATURATED POLYMERS AND COPOLYMERS BYOLEFIN METATHESIS 2 oftheir polymeric main chains. e.g.,1,4-polybutadiene and 1,4-polyisoprene, the olefin metathesis reactionwill lead to the formation of copolymers:

-B-B-B B-B-B- -I-I-I -I-I-I- CH2-CH=CH-CH2 CH -c|:=cH-CH LT CH3 -B-B-BI-I-I- 444 8-3-8- CH2-CH=CH-CH2 ca -p-ca-ca This application is adivision of Application Ser. No. 882,270, filed Dec. 4, 1969, now US.Pat. No. 3,692,872.

The olefin metathesis reaction is a unique bondreorganization process.whereby materials possessing carbon-to-carbon double bonds, undergo aredistribution of constituents as depicted in the following equation:

The sequence length distribution will depend on the extent to which themetathesis reaction is utilized. At the extreme, a random copolymer ofbutadiene and isoprene will be obtained. If the metathesis reaction isutilized to exert only a slight degree of bond reorganization on themixture of the two polymers, the product will be comprised of mainlyblock copolymers of isoprene and butadiene. These products are usefulsince by this process one has considerable control over the sequencedistribution of interpolymers of isoprene and butadiene which are notedfor their good rubbery properties.

When a polymer possessing carbon-to-carbon unsaturation sites in itspendant side groups, e.g., ethylenepropylene-diene terpolymer (EPDM), isexposed to the olefin metathesis reaction in the presence of a secondunsaturated polymer, for example, such as 1,4- polybutadiene, a productcomprised of a graft copolymer of 1,4-polybutadiene on EPDM will beformed:

2R,CH I CHR i R CH CHR. R CH CHR The olefin metathesis reaction, beingan equilibrium process, facilitates: (1) obtaining the olefins R,CH=CHR,and R CH=CHR starting from R,CH=CHR or alternatively. (2) obtaining theolefin R,CH=CHR by starting from a mixture of the olefins R,CH=CHR, andR CH=CHR If the process described in the previous paragraph is appliedto a mixture composed of two polymers, both The graft copolymer ofl,4-polybutadiene on EPDM can be made even more efficiently if the dienetermonomer of the EPDM is an alicyclic compound, such as for example,dicyclopentadiene or 1,5-cyclooctadiene.

having carbon-to-carbon unsaturation in the backbone then the abovereaction becomes in the latter case:

- E) P) (DH-CH (a) [P) 42-543 x 7 m n ca on I 1 cs ca ca=ca 4 r -p I; tc a ca (ai (Pnl ca 11 0 1 c'a -a-a-a-ca -ca=ca CH=CH-CH2-B-B-B- Thesegrafting reactions are sometimes accompanied by gel formation which maybe minimized by incorporating suitable amounts of acyclic unsaturatedcompounds as described in application Ser. No. 882,269 now US. Pat. No.3,754,046 filed on even date herewith.

The catalysts employed in the olefin metathesis process which will bedescribed extensively elsewhere in the present application, are alsocapable of promoting ring-opening polymerization of cycloolefins:

ca on 1 t -t CH a 2 m 0 ca 1 The products obtained as a result of theringopening polymerization of cycloolefinic monomers are polymerspossessing carbon-to-carbon double bonds along the backbone of theirmain polymeric chains. Thus, it can be seen that by reaction at leastone cycloolefinic monomer with at least one of the polymeric species inthe processes described above, a one step" process is obtained whereinthere occurs a simultaneous ringopening polymerization of acycloolefinic monomer and the grafting of the resulting polymer onto asecond backbone" polymer such as EPDM. Likewise, the polymeric speciessuch as EPDM can be grafted onto the polymer resulting from thering-opening polymerization of the cycloolefinic monomer. Polyoctenamer[IUPAC nomenclature, J. Polymer Sci, 8, 257 (1952)leanbcgnfiedonEPDMinamnmrsinilntothe above described grafting of1,4-polybutadiene onto EPDM. Alternatively, a mixture of cyclooctene andEPDM, treated with a catalyst capable ofinducing both olefin metathesisand ring-opening polymerization of cycloolefins will also yield a graftpolymer of polyoctenamer and EPDM. Such a product has good agingstability like EPDM but yet is faster and better curing like dienerubbers.

Similarly by reacting a backbone unsaturated polymer, e.g.,polyoctenamer. with a polymer having both pendant group and backboneunsaturation, e.g., a polybutadiene with mixed 1,4- and 1,2-structures.one may obtain a product which is a combination of graft and blockcopolymer structures.

Another application of the olefin metathesis reaction regardingunsaturated polymers is for the purpose of branching and crosslinking.If an unsaturated polymer, such as 1.4-polybutadiene or polyoctenamer,is exposed to an olefin metathesis catalyst in the presence of certainmulticyclic cycloolefins, containing at least two unsaturated rings,polymerizable by the ringopening process, branching and crosslinking ofthe unsaturated polymer will occur. In general. suitable multicycliccyclomultiolefins will be comprised of 2, 3, 4 or C -ca=cH-ca morering-openable cyclic structures each characterized by an olefinicunsaturation site and the number of carbon atoms occurring in linearsequence in an individual cyclic structure being 4, 5, 8, 9 or more.Examples of typical multi-functional cyclic cross-linking agents arerepresented in the formulae I through IV.

I CIH -(Cl*i l CH OH I l OH CH I II x 1, 2, L 5 or more.

y 1, 2, S or more.

CH H CH cs III IV n m= O, l, 3, l4, 5 or more.

.\ z 1, 2, 4, 5 or more x 1, ,4, 5 or more. u +111 0,1,3, 4,5 or more.

Branching and crosslinking is illustrated for the special case of1,4-polybutadiene and a compound defined by lV where m and :1 both equal2, may be depicted as follows:

-B-B-B -B-B-B- -B-B-B ,B-B-B- ,/CHCH2 CH2 CH2 CHZ-CH CH CH=CH CH CH CH2CH=CH CH CH 7 CH-CH2-CH CH CH CH-CH CH CH l 2 I 2 CH; CH CH CH I I2 2 2CH CH2 ctr CH CH=CH CH -CH CH-CH l 2 l -B-B-B CH2CH=CH-CH2 8-8-8 3-8-8-When this process is carried out extensively, so that on the averageeach weight average chain of L4- polybutadiene participates in onecrosslinking step as described above, the polymer will begin to convertinto an insoluble gel with the introduction of further crosslinking.Such crosslinking converts a raw elastomer into a cured vulcanizate withimproved properties.

If the polymer possesses sufiicient unsaturation in pendant groups thenthe use of an olefin metathesis catalyst may induce crosslinking even inthe absence of crosslinking multicyclic cycloolefins. Additionally,acyclic olefins may be used to diminish the amount of effectivecrosslinking.

It is also possible to replace the unsaturated polymer here by aring-openable cycloolefin so that the ring opening polymerization of acycloolefin in the presence of a multicyclic cyclomultiolefin directlyyields a crosslinked network with useful physical properties. Bycombining polymerization and crosslinking in one step this process isideally suited for making molded products, potting compounds, solidrocket propellents and other products usually made from liquid rubbers.

Polymers that can be employed according to the present invention in thevarious processes. involving the olefin metathesis reaction, for thepurpose of preparing: l copolymers and block copolymers; (2) graftcopolymers; and (3) crosslinking for unsaturated polymers, as have beendescribed heretofore, must possess some carbon-to-carbon double bondunsaturation. Examples are polymers such as polybutadiene, polyisopreneand polyalkenamers corresponding to the formula: [(CH ),,,CH=CH A moregeneral formula of the structural unit occurring in all polymers whichcan be employed in the present invention is the following one which isfree of any non-aromatic conjugation:

where, T is either hydrogen or a substituent group of the structure DCHwherein D is a member se lected from the group consisting of alkyl,aryl, aralkyl. alkaryl, alkenyl, cycloalkyl. cycloalkenyl, bicycloalkyl,bicycloalkenyl radicals and hydrogen; and Z represents hydrogen or afragment having at least one or more carbons and any of the said Zcarbon atoms may be:

a. interconnected by either single or double bonds provided that no twodouble bonds are aliphatically conjugated;

b. any carbon atoms in Z may be substituted by one or more substituentmembers of the group alkyl, aryl, alkenyl, aralkyl, alkenyl, cycloalkyl.cycloalkenyl, bicycloalkyl, and bicycloalkenyl; and any of the carbonatoms in 2 may be constituents of aromatic, alicyclic and chlorinatedalicyclic rings. When V occurs in the polymer backbone, Z ismultifunctional and preferably difunctional. When Z is in a pendentgroup of a polymer, it is preferably monofunctional, such as, hydrogen.alkyl or aryl.

Structural unit V represents the unsaturation sites present in eitherthe backbone or pendent groups of a polymer. Structural unit V may be apolymeric repeat unit of a homopolymer, copolymer or block polymer andas such constitutes unsaturation sites occurring within the backbone ofthe polymer main chain. Examples of such polymers are 1,4-polybutadiene,polyalkenamers, 1,4-po1yisoprene, butyl rubber, SBR (copolymer ofstyrene and butadiene), and a styrenebutadiene-styrene tri-blockcopolymer. Structural unit V may also occur in a pendent group attachedto the backbone of the polymer main chain of a homopolymer, copolymer orgraft polymer. Examples of such polymers are 1,2-polybutadiene,3,4-polyisoprene. 1,2- polypiperylene, EPDM (terpolymer of ethylene,propylene and a non-conjugated diene), and polybutadiene grafted onto abackbone of polystyrene. Structural unit V may be present both in thebackbone and the pendent groups of homopolymers, copolymers and otherinterpolymers. Examples of such polymers are mixed 1,2-,1,4-polybutadiene, SBR with mixed 1,5, 1,4- combined butadiene units andpolybutadiene grafted onto polyisoprene.

Cycloolefins which may undergo ring-opening poly merizations by olefinmetathesis catalysts and are thus useful for the (1) one step" graftingon EPDM. and (2) polymerization and crosslinking in one step, includecompounds selected from the group consisting of:

A. alicyclic compounds corresponding to the formula:

wherein:

l. O is a fragment which comprises a sequence of at least 6 carbon atomssituated in linear succession between the methylidene carbons whichconstitute the double bond;

2. the carbon atoms in the linear succession ofQ may be interconnectedby both carbon-carbon single bonds and carbon-carbon double bonds;

3. any of the carbon atoms in the linear succession of may be sustitutedby at least one member from 1 CH CH wherein:

l. P is a fragment which comprises a sequence of at least 2 and not morethan 3 carbon atoms situated in linear succession between themethylidene carbons which constitute the double bond;

2. the carbon atoms in linear succession of P are connected by carbon tocarbon single bonds;

3. any of the carbons in the linear succession of P may be substitutedby at least one substitutent member from the group of alkyl, aryl.alkenyl, aralkyl, alkaryl. cycloalkyl. cycloalkenyl, bicycloalkyl andbicycloalkenyl radicals;

4. any of said carbons in linear succession of P may be constituents ofaromatic rings, alicyclic rings. and chlorinated alicyclic rings, and

5. said alicyclic unsaturated hydrocarbon compound contains nonon-aromatic conjugated double bonds.

Thus. it can be seen from the foregoing discussion that the process ofthis invention is one of preparing new and novel polymeric materials. Itis also a process for preparing graft interpolymers. It is also aprocess for the preparation of block interpolymers and it is also aprocess of producing branching or crosslinking in an unsaturatedpolymeric material.

Thus, the invention comprises a chemical process involving exposure oftwo or more dissimilar polymeric substances that are characterized bybeing free of any non-aromatic conjugation and comprised of structuralunits of the general formula (V):

wherein: A. T is 1 hydrogen; or

2. a substituent corresponding to the formula DCH:v

where D is any member of the group; alkyl. aryl. aralkyl. alkaryl.alkenyl, cycloalkyl, cycloalkenyl. bicycloalkyl, bicycloalkenyl, andhydrogen; and

B. Z represents hydrogen or a structure having at least one carbon atomand any of the said Z carbons may be:

1. interconnected by single or double bonds;

2. substituted by one or more members of the group alkyl, aryl, aralkyl,alkaryl. alkenyl, cycloalkyl. bicycloalkyl, cycloalkenyl andbicycloalkenyl;

3. constituents of aromatic. alicyclic or chlorinated alicyclic rings;

to a catalyst capable of inducing the olefin metathesis reaction of thedouble bonds of the repeat units of (V leading to products which areinterpolymers of the starting reactant polymeric substances.

The various catalyst systems that have been found to be effective inpromoting the olefin methathesis reaction and the ring-openingpolymerization of unsaturated alicyclic monomers are also effectivecatalyst systems for promoting the processes of the present invention.These catalyst systems may be either heterogeneous or homogeneous withthe former having the advantage of being more readily removable from there action products while the latter is more efficient from thestandpoint of catalytic activity. Catalyst systems which are operableaccording to the present invention are those systems which are capableof promoting the ring opening polymerization of cyclooctene to formpolyoctenamer and/or capable of promoting the olefin metathesis reactionof Z-pentene leading to the formation of Z-butene and 3 hexene attemperatures lower than about C.

One class of homogeneous catalyst systems employed in the practice ofthis invention is a system comprising: (A) at least one organometalliccompound wherein the metal is selected from the group consisting of In,lla, [lb and Illa groups of the Periodic Table of Elements, (B) at leastone metal derivative wherein the metal is selected from the groupconsisting of molybdenum and tungsten and (C) at least one materialselected from a group consisting of oxygen and compounds of the generalformula R-Y-H wherein Y is selected from the group of oxygen and sulfurand wherein R is a radical selected from the group consisting of( lhydrogen. (2) alkyl, (3) aryl, (4) arylalkyl, (5) alkaryl (6) alkenyl.(7) when Y is S R is thioalkyl. thioarylalkyl and thioalkaryl, (8) whenY is O. R is alkoxy. arylalkoxy and alkaryloxy and radicals of (2)through (6) wherein at least one hydrogen is substituted by a groupselected from hydroxyl (OH) and thiol (SH). The Periodic Table ofElements referred to may be found in the Handbook of Chemistry andPhysics, 44th Edition,

April 1962 reprint. published by the Chemical Rubber PublicationCompany. Cleveland Ohio, U.S.A., p. 448.

Representative examples of metals from which the organometalliccompound. the first or (A) component of the catalyst system of thisinvention, can be derived are lithium, sodium, potassium. rubidium,cesium, beryllium, magnesium, calcium. strontium, barium, zinc. cadmium,aluminum, gallium, indium, and thallium. The preferred organometalliccompounds are compounds of lithium, sodium, magnesium, aluminum, zincand cadmium with aluminum being most preferred.

Representative examples of organometallic compounds useful as the firstor (A) catalyst component of this invention are aluminum compoundshaving at least one aluminum-to-carbon bond. Representative of suchcompounds are trialkylaluminums such as trimethylaluminum,triethylaluminum. tri-n-propylaluminum, tri-nbutylaluminum,triisopropylaluminum, triisobutylaluminum, trihexylaluminum,trioctylaluminum, and the like; triarylaluminums such astritolylaluminum, tribenzylaluminum, triphenylaluminum, and the like;dialkylaluminum halides such as diethylaluminum chloride.di-n-propylaluminum chloride, diisobutylaluminum chloride,diethylaluminum bromide, diethylaluminum iodide and diethylaluminumfluoride and the like; mixtures of dialkylaluminum halides andalkylaluminum dihalides such as ethylaluminum sesquichloride andbromides may also be employed; alkylaluminum dihalides such asethylaluminum dichloride. ethylaluminum dibromide, propylaluminumdichloride, isobutylaluminum dichloride, ethylaluminum diiodide and thelike; dialkylaluminum hydrides such as diethylaluminum hydride,di-n-propylaluminum hydride, diisobutylaluminum hydride, and the like;arylaluminum hydrides and dihydrides such as diphenylaluminum hydrideand phenylaluminum dihydride, the arylaluminum halides such asphenylaluminum dibromide, tolylaluminum dibromide, benzylaluminumdibromide, phenylaluminum diiodide, tolylaluminum diiodide,benzylaluminum diiodide, diphenylaluminum chloride, ditolylaluminumchloride, dibenzylaluminum bromide, and the like. Other organometalliccompounds are also useful in the practice of this invention.Representative of such organometallic compounds are organoalkali metalcompounds such as alkyllithium compounds as ethyllithium,n-butyllithium, t-butyllithium and the like;lithium-aluminum-tetraalkyls such as lithiumaluminum tetrabutyl,lithium-aluminum-tetraethyl, and the like; alkali metal alkyls and arylssuch as amylsodium, butylpotassium, phenylpotassium. phenylsodium,phenyllithium, butyllithium and the like; magnesium alkyls and arylssuch as diphenylmagnesium, diethylmagnesium, ethylmagnesium chloride,phenylmagnesium chloride, butylmagnesium bromide, and the like; calcium,strontium and barium organo compounds such as barium alkyls and aryls ofGroups llb metals such as diethylzinc, diphenylzinc, ethylzinc chloride,diethylcadmium, dibutylcadmium, and the like; Grignard agents such asphenylmagnesium bromide may also be employed. Mixtures of thesecompounds may be employed as the first or (A) catalyst component in thecatalyst of this invention. It is usually preferred to employ aluminumcompounds such as trialkylaluminums, dialkylaluminum halides,alkylaluminum dihalides and aluminumsesquihalides.

The metal derivatives employed in the catalyst of this invention as thesecond or (B) catalyst component are selected from the derivatives ofmolybdenum and tungsten. Representatives of such derivatives includehalides such as chlorides, bromides. iodides and fluorides, whichinclude compounds such as molybdenum pentachloride, tungstenhexachloride, molybdenum pentabromide, tungsten haexabromide, molybdenumpentaiodide, molybdenum pentafluoride, molybdenum hexafluoride andtungsten hexafluoride. Other representative salts are those ofacetylacetonates, sulphates. phosphates, nitrates and the like whichinclude compounds such as molybdenum phosphate, tungsten phosphate,molybdenum nitrate, tungsten nitrate, molybdenum acetylacetonate,tungsten acetylacetonate, molybdenum sulphate, and tungsten sulphate.Mixtures of these salts may also be employed. Of these, it is usuallypreferred to employ tungsten halides and molybdenum halides,representative of which are tungsten hexachloride and molybdenumpentachloride.

The third component or (C) component of the catalyst system of thisinvention is selected from the group consisting of oxygen and compoundswhich respond to the formula R-YH wherein Y is selected from the groupconsisting of oxygen and sulfur and R is a radical selected from thegroup consisting of l) hydrogen, (2) alkyl, (3) aryl, (4) arylalkyl, (5)alkaryl. (6) alkenyl, (7) when Y is S, R is thioalkyl, thioarylalkyl andthioalkaryl, (8) when Y is O, R is alkoxy, arylalkoxy and alkaryloxy and(9) radicals of (2) through (6) wherein at least one hydrogen of R issubstituted by at least one hydroxyl (OH) or thio (SH) group.

Thus, the formula RY-H above defines a number of types of compounds. Itdefines water (HOH), hydro gen sulfide (HSH), both saturated andunsaturated alcohols (ROI-l), mercaptans (RSH), hydroperoxides (ROOl-l),hydrodisulfides (RSSH), polyalcohols (HOROH), polymercaptans (HSRSH),and hydroxy mercaptans (HSROH) or thioalcohols (HORSH). Representativeexamples of the materials corresponding to the formula above arealcohols representative of which are methanol, ethanol, isopropanol,tertiarybutyl alcohol, amyl alcohol, benzyl alcohol, allyl alcohol, 1,]-dimethyl benzyl alcohol, phenol, tertiarybutyl catechol, alpha and betanaphthyl alcohol; mercaptans such as methyl, ethyl, propyl, isopropyl,butyl, amyl and similar mercaptans, allyl mercaptan, thiophenol, 4-methylthiophenol, 4mercaptophenol; the hydroperoxides such as cumylhydroperoxide, tertiarybutyl hydroperoxide; the hydrodisulfides such ascumyl hydrodisultide, s-butyl hydrodisulfide; the polyalcohols such asethylene glycol, glycerol, and similar polyglycols; catechol,resorcinol, hydroquinone, pyrogallol; the polymercaptans such as1,3-propane dithiol, 1,4- dithiobenzene; the hydroxymercaptans orthioalcohols such as ethane-2-ol-lthiol, 1-hydroxy-4-thiobenzene.

One of the unusual and distinguishing features of these catalyst systemsis that the compound of the formula R-Y-H, wherein R and Y have beenpreviously defined, when employed in fairly substantial amounts reducesdrastically the activity of the olefin metathesis reaction by which theprocess of this invention occur. These catalyst systems have also beenfound to exhibit unexpected high activity when compounds of the RYH typeare employed in relatively small amounts and added according to theteachings set forth in the present specification and examples. Since theinstant invention contemplates the use of organometallic compounds incombination with transition metal salts and various oxygen andsulfur-containing compounds. and since various factors or considerationswill influence the optimum range of the three catalyst compo nents inrelation to each other. the molar ratios of the three components whichoptimize the reaction conditions cannot be readily set forth. However,by following the teachings found in this application. those skilled inthe art can readily determine the optimum molar ratio of the threecatalyst components to each other. Obviously. if one employs the oxygenor sulfur-containing compound or oxygen or as is designated above. component (C) in relatively large amounts, the activity of the catalyst willbe reduced considerably or even destroyed.

It has been found that good results are obtained in the practice of thisinvention when the molar relationship between the three catalystcomponents. (A). (B) and (C) as previously defined. are within a molarratio of (B)/(C) ranging from about 0.3/1 to at least about /1 and themolar ratio of (A)/(B) is within the range of about 0.5/1 to at least15/1. More preferred ratios are (Bl/(C) of0.5/I to 5/1 and (A)/(B)of0.5/1 to 8/1. Still more preferred ratios were (B)/(C) of 1/1 to 2/1and (A)/(B) of 0.75/1 to 5/1.

The catalyst systems set forth above and useful in the practice of thisinvention are prepared by mixing the components by known techniques.Thus, the catalyst systems may be prepared by preformed or "in situ"techniques. By the preformed" method the catalyst components are mixedtogether prior to exposure of any of the catalyst components to beunsaturated reactants to be used in the process of this invention. Inthe in situ method the catalyst components are added separately to theunsaturated reactants to be used in the process of this invention. Thecatalyst components may be mixed either as pure compounds or assuspensions or solutions in liquids which do not adversely affeet thecatalyst activity of the olefin metathesis reac tion. Representative ofsuch liquids are saturated hydrocarbons such as hexane. pentane and thelike, or aromatics such as benzene. toluene and the like.

While the presence of the unsaturated reactants is not essential duringthe formation of active catalyst by a mixing of components (A), (B) and(C) and this fact facilitates the use ofpreformed" catalysts, it hasbeen found that freshly preformed catalysts are generally more activethan catalysts which have been allowed to age before use.

The order of addition of the three catalyst components to each other isof interest in the practice of this invention There are various methodsin which the three catalyst components can be brought into contact withthe reactants or reactants/solvent mixture. The follow' ing is anumerical listing of these various methods in which A. B and C stand forthe catalyst components as previously defined:

l. Simultaneous addition of A. B and C;

2. C followed by A and B which were previously preformed;

3. A and B performed followed by C:

4 A followed by B and C which were performed;

5. B and C preformed followed by A;

6. B followed by A and C which were preformed;

7. A and C preformed followed by B;

8. A followed by B followed by C;

9. B followed by A followed by C;

10. C followed by B followed by A;

11. C followed by A followed by B;

12. B followed by C followed by A;

13. A followed by C followed by B;

14. Preformed A. B and C which was prepared by adding A to B and Cpreformed;

15. Preformed A, B and C which was prepared by adding B to A and Cpreformed; and

16. Preformed A, B and C which was prepared by adding C to A and Bpreformed.

The amount of catalyst employed in the reactions of this invention maybe varied over wide concentrations and has not been found to becritical. Of course. a catalyst amount of the catalyst must be employed.The optimum amount of catalyst depends upon a number of factors such astemperature, purity of reactants. reaction times desired. and the like.the processes of this invention can be conducted wherein the amount ofcatalyst employed is about 0.01 part by weight of component (B) perparts by weight of unsaturated reactants employed. with components (A)and (C) adjusted to yield a desirable molar ratio of (A)/(B)/(C). Thoseskilled in the art will readily be able to determine the optimumcatalytic ranges.

A second class of catalyst systems effective in the present inventionconsists of a two-component catalyst system. This catalyst systemcomprises (A) at least one organoaluminum halide selected from the groupconsisting of RAIX and R AlX wherein X is a halide such as chloride.bromide, iodide, and fluoride, and R is selected from the group ofalkyl, aryl, arylalkyl and alkaryl. and (B) at least one tungstenderivative.

Thus. representative examples of the first or (A) catalyst component arealuminum compounds having at least one aluminum-to-carbon bond.Representative of such compounds are dialkylaluminum halides such asdiethylaluminum chloride, di-n-propylaluminum chloride.diisobutylaluminum chloride, diethylaluminum bromide. diethylaluminumiodide and diethylaluminum fluoride. and the like; mixtures ofdialkylaluminum halides and alkylaluminurn dihalides such asethylaluminum sesquichloride and bromides may also be employed;alkylaluminum dihalides such as ethylaluminum dichloride, ethylaluminumdibromide. propylaluminum dichloride. isobutylaluminum dichloride.ethylaluminum diiodide. and the like; the arylaluminum halides such asphenylaluminum dibromide, tolylaluminum dibromide. benzylaluminumdibromide, phenylaluminum diiodide, tolylaluminum diiodide,benzylaluminum diiodide, diphenylaluminum chloride, ditolylaluminumchloride, dibenzylaluminum bromide. and the like.

Representative of the tungsten salts employed as the second or (B)catalyst component include halides such as chlorides, bromides, iodides,and fluorides. which include compounds such as tungsten hexachloride,tungsten hexabromide. tungsten hexaiodide, and tungsten hexafluoride.Other representative salts are those of acetylacetonates. sulphates,phosphates, nitrates. and the like which include compounds such astungsten phosphate. tungsten nitrate. tungsten acetylacetonate andtungsten sulphate. Mixtures of these salts may also be employed. Ofthese. it is usually preferred to employ tungsten halides such astungsten hexachloride.

The molar relationship between the two catalyst components (A) and (B)as previously defined in this catalyst system are within a molar ratioof (A)/(B) of about 0.5/1 to about 15/1 with a more preferred molarratio of (Al/(B) of about 0.5/1 to about 8/1 and a still more preferredmolar ratio of (A)/(B) of about 0.75/1 to about /1. These catalysts canbe prepared by in situ" or preformed" techniques. No particular order ofaddition is required in preparing active catalysts from this species.These catalyst components may be reacted together as pure compounds orin solutions or suspensions in inert liquids. Representative of suchliquids are saturated hydrocarbons such as pentane. hexane and the likeor aromatic hydrocarbons such as benzene. toluene and the like.

The amount of catalyst employed in the reactions of the presentinvention, when this two-component catalyst system is employed. has notbeen found to be critical and may range over wide concentrations. Ofcourse. a catalytic amount of the catalyst must be employed but theoptimum amount depends upon a number of factors such as temperatureemployed. the particular reactants employed. the purity of thereactants. the reaction times desired. and the like. Polymerizationreactions can be conducted wherein the amount of catalyst is about 0.01part by weight of the (B) component per 100 parts by weight of themonomer employed with the proper mole ratio of (A)/(B) being adjusted.

A third class of catalyst systems effective in promoting the processesof the present invention consists of (A) an aluminum halide, AlX=,. and(B) a salt of the transition metal tungsten. whereby the tugnsten is atany oxidation status within the 1V and V1 range.

Representative examples of component (A) are: aluminum chloride.aluminum bromide, aluminum iodide and aluminum fluoride. The preferredhalides are the chloride and bromide of aluminum. Examples of component(B) are: tungsten. tetra-. pentaand hexachloride, tungsten tetra-andpentabromide, tungsten tetraand pentaiodide. tungsten hexafluoride andthe tungsten oxychlorides. This two component catalyst system is uniqueas it does not require the employement of any organometallic catalystcomponent. However, this system can be further modified by anorganometallic reagent. In certain reactions of unsaturated alicycliccompounds. advantages such as suppression of gel formation. and anincrease in polymerization rates at low catalyst levels can be achievedby the modification of the last two-component catalyst system by anoptional third organometallic reagent). Examples of such optionalorganometallic reagents are organoalkali metal compounds such as alkyland aryllithium; alkyland arylsodium; organ-magnesium compounds such asdialkylor diarylmagnesium; organomagnesium halides; organometallicderivatives of calcium, strontium and barium; alkyls and aryls of GroupslIb metals such as dialkyl and diarylzinc and the like.

Other classes of catalysts which are effective in promoting thepolymerizations of this invention are those disclosed in U.S. Pat.Applications Ser. Nos. 755,374 now U.S. Pat. No. 3,689,471; 755,375abandoned. refiled as Ser. No. 86,002, now U.S. Pat. No. 3,657,208;755,376 now U.S. Pat. No. 3,577,400 and 795,693 now U.S. Pat. No.3,624,060.

The operating conditions which are employed in the processes of thisinvention may vary. The reactions can be conveniently carried out in aliquid form or even only a swollen system. Thus. when a polymericmaterial is employed in any particular reaction. it is possible to carryout the reaction in solution. Solvents which can be used when solutionconditions are employed include any inert solvents that preferablydissolve or swell the polymers employed. Convenient solvents arealiphatic, aromatic or cycloaliphatic hydrocarbons which do notthemselves inhibit or interfere with the metathesis reaction. such aspentane. hexane. benzene. toluene. cyclohexane and the like. When thereactants are liquid. the reaction can be conducted in bulk.

Since the present invention teaches the preparation of crosslinkedpolymers in a one-step process starting with a cycloolefin monomer inthe presence of multifunctional crosslinking polycyclicpolyenecomonomers. there is within the scope of this invention a processwhereby a mixture containing (a) polymerizable unsaturated alicyclicmonomer; (b) a multifunctional crosslinking comonomer; (c) a filler;(cl) antioxidant; and (e) extending oil. is exposed to a suitable olefinmethathesis catalyst obtaining a mixture which can be polymerized in amold to a crosslinked finished rubber product, all in one step. When thefiller used is a reinforcing carbon black or iron oxide pigment. theresulting product is useful in many mechanical rubber goodsapplications. When the filler is capable of an exothermic reaction.e.g., an oxidizing mixture. such as ammonium perchlorate and powderedaluminum, the product is a solid rocket propellant.

The metathesis processes involved in this invention can be carried outover a wide range of temperatures. It is convenient to carry out theprocess at room temperature.

The invention is further illustrated by reference to the followingexamples which are intended to be representative rather than restrictiveof the scope of this invention.

EXAMPLE 1 A solution of ml cyclooctene in 1400 ml benzene waspolymerized at 30 C. using 4.0 ml of WCl C H OH (0.05M) and 4.0 ml ofethylaluminum dichloride (EADC) (0.2 M) as the catalyst. In a separatepolymerization reaction. 30 ml cyclododecene was polymerized in 300 mlbenzene using 2.0 ml WCl.,-C H,,OH (0.05 M) and 2.0 ml of EADC (0.2 M).After about 30 minutes, during which both polymerizations reached highconversions, the viscous cements of the cyclooctene and cyclododecenepolymerizations were mixed. An additional 4.0 ml WCl.,'C H,-,OH (0.05 M)and 4.0 ml EADC (0.2 M) solutions were added. allowing both polymers tointer-react for about five minutes before terminating with methanolcontaining di-tert.-butyl-p-cresol antioxidant. After drying andisolation of the product, a final yield of 81.0 gins of a copolymer ofcyclooctene and cyclododecene was obtained. The product had physicalcharacteristics suggesting that it was substantially a block copolymerof the reacting polymers.

EXAMPLE 11 An 18 gm EPDM sample (Nordel 1070 DuPonts trade name) wasdissolved in 450 ml dry benzene, containing 20 ml of 1,5-cyclooctadiene(COD). and purged with nitrogen for 10 minutes. A solution of 4.0

ml WCl -C H5OH (0.05M) was added followed by 4.0 ml of EADC (0.2 M).After about five minutes the cement thickened and converted to acrosslinked gel. The mixture was treated with methanol containingdi-tertbutyl-p-cresol and tray-dried. A yield of 31 grams of graftcopolymer of polybutadiene (polybutenamer) on EPDM was obtained EXAMPLElll Two EPDM (Nordel 1070) samples (90 gms each) were separatelydissolved in 3.5 liters of benzene. each containing ml of B-heptene. Onebottle was charged with 22.5 gms and the other with 45.0 gms of 1.5-cyclooctadiene. Polymerization and grafting were promoted with the WClfi-C2H OH and EADC catalyst combinations. in a similar manner as inExample II. The products of reaction did not gel in these experimentsand the graft copolymers were found to be soluble. NMR analyses of thepolymers indicated a level of unsaturation corresponding to weightpercent polybutadiene grafted on the EPDM.

EXAMPLE IV Into a 20 gm sample of purified cyclooctene there was added0.06 gms of cyclooctadienecyclopentadiene dimer (CODCPD) having thestructural formula:

The mixture was thoroughly purged by nitrogen. then treated by 1 ml ofWClhsolution in benzene (0.05M), followed by 1 ml EADC solution (0.2 M).The mixture turned viscous within a matter of a few seconds. Afterminutes the polymerizing mass became a rubbery solid. The reactionproduct was found to be 98.2% insoluble in benzene. and the insolublegel had a swelling ratio in benzene of 5.2 (Swelling ratio Wt. ofswollen rubber! Wt. of dried rubber).

EXAMPLE V EXAMPLE Vl Into a solution of 8 gms of polybutadiene(polybutenamer) in X00 ml benzene there is added 8 gms of c cclooctenemonomer. The mixture is thoroughly Shaken and purged with dry nitrogen.A catalyst, comprising i ml WCl 'C- H OH (0.05 M) and 1 ml EADC (0.2 Mlsolutions in benzene. is added to the mixture. The reaction is allowedto proceed at room temperature for about 30 minutes. whereupon anapproximately /50 poly(butenamer-cooctenamer) is obtained. The prod notis isolated after termination by tray-drying. lt appeared to be a randomcopolymer of butenamer and octenamer units.

EXAMPLE Vll A. Preparation of Polymerizing Dispersions Cyclooctene.freshly distilled from sodium. was mixed with an extender oil (Shellflex310 the antioxidant di-tertbutyl-p-cresol. and carbon black filler in aclean. dry. balljar under nitrogen for sixteen hours. Prior to use. thecarbon black was degassed by warming at C.-80C. under vacuum for aperiod of four hours.

B. Polymerization Procedure lnto each of the 8 02. bottles. fitted withself-sealing caps. 40 ml premix (prepared as described in A) wasintroduced. Varied amounts of COD-CPD (see Example VI) were added to thebottles prior to purging with nitrogen. The capped bottles were injectedwith the catalyst components (WClGC I-I OH and EADC) which weredissolved in high boiling oils. The bottles were placed on rotatingrollers for 30 minutes causing the polymerization product to form sheetsof crosslinked. carbon black filled. oil extended polyoctenamer rubberon the walls of the bottles. The resulting sheets were placed in avacuum oven for drying.

Dumbbells were cut out of the rubber sheets and tensile strengthmeasurements were carried out. The relevant data of these experimentsare included in Table 1.

Table l Elong Exp. Conver- COD.CPD* Modulus Tensile ation No. sion(7r(Phr) (300%.psi) (psi) premix contained 1H phm (pans per hundredmonomer) FEF carbon black. 25 phm Shcllflcx 3 It] oil. and l phmditerL-hutyl-p-crcsol antioxidant wherein:

(AlT is 1. hydrogen: or

2. a substituent corresponding to the formula DCH where D is any memberof the group: alkyl. aryl. aralkyl, alkaryl, alkenyl. cycloalkyl.cycloalkenyl. bicycloalkyl, bicycloalkenyl. and hydrogen; and

B. Z represents hydrogen or a structure having at least one carbon atomand any of the said Z carbons may be:

1. interconnected by single or double bonds;

2. substituted by one or more members of the group alkyl. aryl. aralkyl.alkaryl. alkenyl. cycloalkyl. bicycloalkyl. cycloalkenyl andbicycloalkenyl;

3. constituents of aromatic. alicyclic or chlorinated alicyclic rings;

to a catalyst capable of inducting the olefin metathesis reaction and ofinducing ring-opening polymerization. said catalyst which will convertZ-pentene into 2- butene and 3-hexene at temperatures lower than about100C, leading to products which are interpolymers of 20 the startingreactant polymeric substances.

2. The process of claim 1 whereby the catalyst is derived from:

A. a salt or a coordination compound of the transition metals tungstenand molybdenum, and

B. an organometallic compound or an organoaluminum halide or an aluminumhalide, in which the molar relationship between the catalyst componentsis within the molar ration f(A)/(B) of about 0.5 to l to about lS/l.

3. The process of claim 1 wherein the catalyst is a mixture of:

A. at least one organometallic compound wherein the metal is selectedfrom the group consisting of la. Ila, [lb and Illa of the Periodic Tableof Elements.

B. at least one metal derivative wherein the metal is selected from thegroup consisting of tungsten and molybdenum, and

C. at least one specie selected from the group consisting of oxygen andcompounds of the general formula RYH wherein Y is selected from thegroup of oxygen and sulfur and wherein R is a radical selected from thegroup consisting of( l hydrogen, (2) alkyl, (3) aryl, (4) arylalkyl, (5)alkaryl. (6) alkenyl, (7) when Y is S, R is thioalkyl, thioarylalkyl andthioalkaryl, (8) when Y is O, R is alkoxy, arylalkoxy and alkaryloxy andradicals of (2) through (6) wherein at least one hydrogen is substitutedby a group selected from hydroxyl (OH) and thiol (SH) in which the molarrelationship between the catalyst components is within the molar ratioof (Bl/(C) ranging from about 0.3/1 to about /1 and the molar ratio of(A)/(B) is within the range of about 0.5/l to about 15/1.

4. The process of claim 1 wherein the catalyst is a mixture of:

A. at least one organoaluminum halide selected from the group consistingof RAIX and R- ,AlX wherein X is a halide and R is selected from thegroup of alky], aryl, arylalkyl and alkaryl, and

B. at least one tungsten derivative. in which the molar relationshipbetween the catalyst components is within the molar ration of (A)/(B) ofabout 0.5 to l to about 15/1. 5. The process of claim 1 wherein thecatalyst is a mixture of:

A. an aluminum halide of the formula AlX and B. a salt of tungstenwherein the tungsten is in an oxidation state within the IV to Vl rangein which. the molar relationship between the catalyst components iswithin the molar ratio of (Al/(B) of about 0.5 to l to about lS/l. 6.The process of claim 1 wherein a mixture comprismg A. an terpolymer andB. a polymer having a structure (VI) or Vll):

1. Q is a fragment which comprises a sequence of at least 6 carbon atomssituated in linear succession between the methylidene carbons whichconstitute the double bond;

2. the carbon atoms in the linear succession of 0 may be interconnectedby both carbon-carbon single bonds and carbon-carbon double bonds;

3. any of the carbon atoms in the linear succession of Q may besubstituted by at least one member from the group of alkyl, aryl.alkenyl, aralkyl, alkaryl. cycloalkyl, cycloalkenyl, bicycloalkyl andbicycloalkenyl radicals;

4. any of said carbon atoms in the linear succession of Q may beconstituents of aromatic rings, alicyclic and chlorinated alicyclicrings; and

5. said polymer of structure (Vl) contains no nonaromatic conjugateddouble bonds;

and wherein:

l. P is a fragment which comprises a sequence of at least 2 and not morethan 3 carbon atoms situated in linear succession between themethylidene carbons which constitute the double bond;

2. the carbon atoms in linear succession of P are connected by carbon tocarbon single bonds;

3. any of the carbons in the linear succession of P may be substitutedby at least one substituent member from the group of alkyl, aryl,alkenyl, aralkyl, alkaryl, cycloalkyl. cycloalkenyl, bicycloalkyl andbicycloalkenyl radicals;

4. any of said carbons in linear succession of P may be constituents ofaromatic rings and alicyclic rings, and

5. said polymer of structure (Vll) contains no nonaromatic conjugateddouble bonds.

is exposed to a catalyst capable of inducing the olefin metathesisreaction of the double bonds, leading to interpolymeric products of VIor Vll and terpolymers.

7. The process of claim 6 wherein the unsaturated reactant is apolymeric material member of the group: polybutadiene,isoprene-butadiene copolymer and butadiene-styrene copolymers.

8. Composition of matter of polybutadiene grafted onto an terpolymer.

9. Composition of matter of polyoctenamer grafted onto an terpolymer.

PATENT NO.

DATED INVENTOR(S) I Col. 2

Col. C01. C01.

Colo C01.

Col.

smu

UNITED STATES PATENT OFFICE June 2 1975 Scott, Kenneth W, Calderon,Nissim It is certified that error appears in the above-identified patentand that said Letters Patent are hereby corrected as shown below:

55, insei't rrows in formula Nos. 3 & "performed" should be "preformed".

2, lines 15-1 1. i talye?" eeld ,b 'i y isf-" line 5 "organshould'be "arued", line 24, "C should be "C claim 1, li 57, "conjunction" should be"conjugation".

line 16, "inducting" should be "inducing". line 12,- Claim 6 (A) afterthe word "an" should be --[ethylene-propylene-diene]--.

line 5h, Claim 6, after the word "an" should be--[ethylene-propylene-diene]: line 60, Claim 8, after the word "and" Ushould be [ethylene-propylene-l, r-hexadiene]--. line 62, Claim 9, afterthe word "an" should be [ethylene-propylene-l,h-hexadiene]-.

Signed and Scaled this Twenty-first Day of Aprill98i Aunt:

RENE D. TEGTMEYER Arresting Oflicer Acting Commissioner of Patents andTrademarks

1. A CHEMICAL PROCESS INVOLVING EXPOSURE OF TWO OR MORE DISSIMILARPOLYMERIC SUBSTANCES THAT ARE CHARACTERIZED BY BEING FREE OF ANYNON-AROMATIC CONJUCTION AND COMPRISED OF STRUCTURAL UNITS OF THE GENERALFORMULA (V):
 1. INTERCONNECTED BY SINGLE OR DOUBLE BONDS;
 2. SUBSTITUTEDBY ONE OR MORE MEMBERS OF THE GROUP ALKYL, ARYL, ARALKYL, ALKARYL,ALKENYL, CYCLOALKYL, BICYCLOALKYL, CYCLOALKENYL AND BITYCLOALKEMYL, 2.substituted by one or more members of the group alkyl, aryl, aralkyl,alkaryl, alkenyl, cycloalkyl, bicycloalkyl, cycloalkenyl andbicycloalkenyl;
 2. a substituent corresponding to the formula D-CH2-,where D is any member of the group: alkyl, aryl, aralkyl, alkaryl,alkenyl, cycloalkyl, cycloalkenyl, bicycloalkyl, bicycloalkenyl, andhydrogen; and B. Z represents hydrogen or a structure having at leastone carbon atom and any of the said Z carbons may be:
 2. the carbonatoms in linear succession of P are connected by carbon to carbon singlebonds;
 2. A SUBSTITUENT CORRESPONDING TO THE FORMULA D-CH2-, WHERE D ISANY MEMBER OF THE GROUP: ALKYL, ARYL, ARALKYL, ALKARYL, ALKENYL,CYCLOALKYL, CYCLOALKENYL, BICYCLOALKYL, BICYCLOALKENYL, AND HYDROGEN,AND B. Z REPRESENTS HYDROGEN OR A STRUCTURE HAVING AT LEAST ONE CARBONATOM AND ANY OF THE SAID Z CARBONS MAY BE:
 2. the carbon atoms in thelinear succession of Q may be interconnected by both carbon-carbonsingle bonds and carbon-carbon double bonds;
 2. The process of claim 1whereby the catalyst is derived from: A. a salt or a coordinationcompound of the transition metals tungsten and molybdenum, and B. anorganometallic compound or an organoaluminum halide or an aluminumhalide, in which the molar relationship between the catalyst componentsis within the molar ration of (A)/(B) of about 0.5 to 1 to about 15/1.3. any of the carbon atoms in the linear succession of Q may besubstituted by at least one member from the group of alkyl, aryl,alkenyl, aralkyl, alkaryl, cycloalkyl, cycloalkenyl, bicycloalkyl andbicycloalkenyl radicals;
 3. any of the carbons in the linear successionof P may be substituted by at least one substituent member from thegroup of alkyl, aryl, alkenyl, aralkyl, alkaryl, cycloalkyl,cycloalkenyl, bicycloalkyl and bicycloalkenyl radicals;
 3. constituentsof aromatic, alicyclic or chlorinated alicyclic rings; to a catalystcapable of inducting the olefin metathesis reaction and of inducingring--opening polymerization, said catalyst which will convert 2-penteneinto 2-butene and 3-hexene at temperatures lower than about 100*C,leading to products which are interpolymers of the starting reactantpolymeric substances.
 3. The process of claim 1 wherein the catalyst isa mixture of: A. at least one organometallic compound wherein the metalis selected from the group consisting of Ia, IIa, IIb and IIIa of thePeriodic Table of Elements. B. at least one metal derivative wherein themetal is selected from the group consisting of tungsten and molybdenum,and C. at least one specie selected from the group consisting of oxygenand compounds of the general formula R-Y-H wherein Y is selected fromthe group of oxygen and sulfur and wherein R is a radical selected fromthe group consisting of (1) hydrogen, (2) alkyl, (3) aryl, (4)arylalkyl, (5) alkaryl, (6) alkenyl, (7) when Y is S, R is thioalkyl,thioarylalkyl and thioalkaryl, (8) when Y is O, R is alkoxy, arylalkoxyand alkaryloxy and radicals of (2) through (6) wherein at least onehydrogen is substituted by a group selected from hydroxyl (OH) and thiol(SH) in which the molar relationship between the catalyst components iswithin the molar ratio of (B)/(C) ranging from about 0.3/1 to about 20/1and the molar ratio of (A)/(B) is within the range of about 0.5/1 toabout 15/1.
 3. CONSTITUENTS OF AROMATIC, ALICYCLIC OR CHLORINATEDALICYCLIC RINGS, TO A CATLYST CAPABLE OF INDUCTING THE OLEFIN METAHESISREACTION AND OF INDUCING RING-OPENING POLYMERIZATION, SAID CATALYSTWHICH WILL CONVERT 2-PENTENE INTO 2-BUTENE AND 3-HEXENE AT TEMPERATURESLOWER THAN ABOUT 100*C, LEADING TO PRODUCTS WHICH ARE INTERPOLYMERS OFTHE STARTING REACTANT POLYMERIC SUBSTANCES.
 4. The process of claim 1wherein the catalyst is a mixture of: A. at least one organoaluminumhalide selected from the group consisting of RAlX2 and R2AlX wherein Xis a halide and R is selected from the group of alkyl, aryl, arylalkyland alkaryl, and B. at least one tungsten derivative, in which the molarrelationship between the catalyst components is within the molar rationof (A)/(B) of about 0.5 to 1 to about 15/1.
 4. any of said carbon atomsin the linear succession of Q may be constituents of aromatic rings,alicyclic and chlorinated alicyclic rings; and
 4. any of said carbons inlinear succession of P may be constituents of aromatic rings andalicyclic rings, and
 5. said polymer of structure (VII) contains nononaromatic conjugated double bonds, is exposed to a catalyst capable ofinducing the olefin metathesis reaction of the double bonds, leading tointerpolymeric products of VI or VII and terpolymers.
 5. said polymer ofstructure (VI) contains no nonaromatic conjugated double bonds; andwherein:
 5. The process of claim 1 wherein the catalyst is a mixture of:A. an aluminum halide of the formula AlX3 and B. a salt of tungstenwherein the tungsten is in an oxidation state within the IV to VI rangein which, the molar relationship between the catalyst components iswithin the molar ratio of (A)/(B) of about 0.5 to 1 to about 15/1. 6.The process of claim 1 wherein a mixture comprising A. an terpolymer andB. a polymer having a structure (VI) or VII): (Q - CH CH - )-(VI) (P- CHCH - )- (VII) wherein:
 7. The process of claim 6 wherein the unsaturatedreactant is a polymeric material member of the group: polybutadiene,isoprene-butadiene copolymer and butadiene-styrene copolymers. 8.Composition of matter of polybutadiene grafted onto an terpolymer. 9.Composition of matter of polyoctenamer grafted onto an terpolymer.